Quaternary ammonium salt of a mannich compound

ABSTRACT

A quaternary ammonium salt detergent made from the reaction product of the reaction of: (a) Mannich reaction product having a tertiary amino group, said Mannich reaction product being prepared from the reaction of a hydrocarbyl-substituted phenol, an aldehyde, and amine; and (b) a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen and the use of such quaternary ammonium salt detergents in a fuel composition to reduce intake valve deposits.

This application is a divisional of prior application U.S. Ser. No.11/469,690 filed Sep. 1, 2006 and claims the benefit of said priorapplication.

BACKGROUND OF THE INVENTION

The composition of the present invention relates to a quaternaryammonium salt detergent and the use of such quaternary ammonium saltdetergents in a fuel composition to reduce intake valve deposits andremove or clean up existing deposits on the intake valves; and the useof the quaternary ammonium salt in media such as inks, coatings,mill-bases, plastics and paints. For this application the termsdetergent and dispersant can be used interchangeable and have the samemeaning.

It is well known that liquid fuel contains components that can degradeduring engine operation and form deposits. These deposits can lead toincomplete combustion of the fuel resulting in higher emission andpoorer fuel economy. Fuel additives, such as detergents, are well knownadditives in liquid fuels to help with control or minimize depositformation. As the dynamics and mechanics of an engine continual advance,the requirements of the fuel must evolve to keep up with these engineadvancements. For example, today's engines have injector system thathave smaller tolerances and operate at higher pressure to enhance fuelspray to the compression or combustion chamber. Deposit prevention anddeposit reduction in these new engines has become critical to optimaloperation of today's engines. Advancements in fuel additive technology,such as detergents, have enabled the fuel to keep up with these engineadvancements. Therefore, there is a need for detergent capable ofproviding acceptable performance in a liquid fuel to promote optimaloperation of today's engines.

U.S. Pat. No. 5,000,792 discloses polyesteramine detergent obtainable byreacting 2 parts of polyhydroxycarboxylic acids with 1 part ofdialkylenetriamine.

U.S. Pat. No. 4,171,959 discloses a motor fuel composition containingquaternary ammonium salts of a succinimide. The quaternary ammonium salthas a counterion of a halide, a sulphonate or a carboxylate.

U.S. Pat. Nos. 4,338,206 and 4,326,973 discloses fuel compositionscontaining a quaternary ammonium salt of a succinimide, wherein theammonium ion is heterocyclic aromatic (pyridinium ion).

U.S. Pat. No. 4,108,858 discloses a fuel or lubricating oil compositioncontaining a C2 to C4 polyolefin with a Mw of 800 to 1400 salted with apyridinium salt.

U.S. Pat. No. 5,254,138 discloses a fuel composition containing areaction product of a polyalkyl succinic anhydride with a polyaminohydroxyalkyl quaternary ammonium salt.

U.S. Pat. No. 4,056,531 discloses a lubricating oil or fuel containing aquaternary ammonium salt of a hydrocarbon with a Mw of 350 to 3000bonded to triethylenediamine. The quaternary ammonium salt counterion isselected from halides, phosphates, alkylphosphates, dialkylphosphates,borates, alkylborates, nitrites, nitrates, carbonates, bicarbonates,alkanoates, and O,O-dialkyldihtiophosphates.

U.S. Pat. Nos. 4,253,980 and 4,306,070 disclose a fuel compositioncontaining a quaternary ammonium salt of an ester-lactone.

U.S. Pat. No. 3,778,371 discloses a lubricating oil or fuel containing aquaternary ammonium salt of a hydrocarbon with a Mw of 350 to 3000; andthe remaining groups to the quaternary nitrogen are selected from thegroup of C1 to C20 alkyl, C2 to C8 hydroxyalkyl, C2 to C20 alkenyl orcyclic groups.

The present invention, therefore, promotes optimal engine operation,that is, increased fuel economy, better vehicle drivability, reducedemissions and less engine maintenance by reducing, minimizing andcontrolling deposit formation.

Many formulations such as inks, paints, mill-bases and plasticsmaterials require effective dispersants for uniformly distributing aparticulate solid in an organic medium. The organic medium may vary froma polar to non-polar organic medium. Dispersants containing terminalbasic groups such as poly(lower alkylene)imine chains are well known andare generally prepared by reaction of the polyimine with polyesterchains containing terminal acid groups, the reaction results in amixture of amide and salt forms. However, many of these dispersants havelimited performance towards viscosity and stability properties, whichwhen incorporated into printing inks or paints give the inks and paintswith poor flow characteristics. Therefore, there is a need for adispersant capable of providing acceptable flow characteristics andhaving stability properties.

U.S. Pat. No. 5,721,358 which discloses a process for copperphthalocyanine production using a dispersant derived from a non-saltedsuccinimide dispersant. The succinimide dispersant is derived from analkyleneamine and polyisobutylene succinic anhydride.

US Application 2003/0213410 discloses a polymer-modified pigmentcomprising a polymer with at least one carboxylic group or salt thereofand at least one coupling agent. The polymer includes derivatives ofpolyamines that have been reacted with an acylating agent such as aceticor succinic anhydride.

GB 1,373,660 discloses polyesteramine dispersants obtainable by reactionof polyhydroxycarboxylic acids with diamines especially alkylenediaminesand their salts thereof.

Therefore, it would be advantageous to have a dispersant with acceptableperformance, which when incorporated into inks, coatings, mill-bases,plastics and paints gives the inks, coatings, mill-bases, plastics orpaints acceptable flow characteristics.

SUMMARY OF THE INVENTION

The present invention provides a composition comprising a quaternaryammonium salt which comprises the reaction product of:

a. Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The present invention further provides a method for fueling an internalcombustion engine, comprising:

A. supplying to said engine:

-   -   i. a fuel which is liquid at room temperature; and    -   ii. quaternary ammonium salt comprising the reaction product of:        -   a. Mannich reaction product having a tertiary amino group,            said Mannich reaction product being prepared from the            reaction of a hydrocarbyl-substituted phenol, an aldehyde,            and an amine; and        -   b. a quaternizing agent suitable for converting the tertiary            amino group to a quaternary nitrogen.

The present invention additionally provides a method of lubricating aninternal combustion engine comprising:

A. supplying to the crankcase of said engine:

-   -   i. an oil of lubricating viscosity; and    -   ii. quaternary ammonium salt comprising the reaction product of:        -   a. Mannich reaction product having a tertiary amino group,            said Mannich reaction product being prepared from the            reaction of a hydrocarbyl-substituted phenol, an aldehyde,            and amine; and        -   b. a quaternizing agent suitable for converting the tertiary            amino group to a quaternary nitrogen.

The present invention further provides a composition comprising: (i) aparticulate solid; (ii) an organic medium; and (iii) a quaternaryammonium salt which comprises the reaction product of:

a. Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The present invention further provides a paint or ink compositioncomprising a particulate solid, an organic liquid, a binder and aquaternary ammonium salt which comprises the reaction product of:

a. Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The present invention further provides a mill-base comprising aparticulate solid, an organic liquid and a quaternary ammonium saltwhich comprises the reaction product of:

a. Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

Field of the Invention

This invention involves a quaternary ammonium salt, a fuel compositionthat includes the quaternary ammonium salt, and a method of operating aninternal combustion engine with the fuel composition. The compositionsand methods of the present invention minimize, reduce and controldeposit formation in the engine, which reduces fuel consumption,promotes drivability, vehicle maintenance, and reduces emissions whichenables optimal engine operation.

Fuel

The composition of the present invention can comprise a fuel which isliquid at room temperature and is useful in fueling an engine. The fuelis normally a liquid at ambient conditions e.g., room temperature (20 to30° C.). The fuel can be a hydrocarbon fuel, a nonhydrocarbon fuel, or amixture thereof. The hydrocarbon fuel can be a petroleum distillate toinclude a gasoline as defined by ASTM specification D4814 or a dieselfuel as defined by ASTM specification D975. In an embodiment of theinvention the fuel is a gasoline, and in other embodiments the fuel is aleaded gasoline, or a nonleaded gasoline. In another embodiment of thisinvention the fuel is a diesel fuel. The hydrocarbon fuel can be ahydrocarbon prepared by a gas to liquid process to include for examplehydrocarbons prepared by a process such as the Fischer-Tropsch process.The nonhydrocarbon fuel can be an oxygen containing composition, oftenreferred to as an oxygenate, to include an alcohol, an ether, a ketone,an ester of a carboxylic acid, a nitroalkane, or a mixture thereof. Thenonhydrocarbon fuel can include, for example, methanol, ethanol, methylt-butyl ether, methyl ethyl ketone, transesterified oils and/or fatsfrom plants and animals such as rapeseed methyl ester and soybean methylester, and nitromethane. In several embodiments of this invention thefuel can have an oxygenate content on a weight basis that is 1 percentby weight, or 10 percent by weight, or 50 percent by weight, or up to 85percent by weight. Mixtures of hydrocarbon and nonhydrocarbon fuels caninclude, for example, gasoline and methanol and/or ethanol, diesel fueland ethanol, and diesel fuel and a transesterified plant oil such asrapeseed methyl ester. In an embodiment of the invention, the liquidfuel can be an emulsion of water in a hydrocarbon fuel, a nonhydrocarbonfuel, or a mixture thereof. In several embodiments of this invention thefuel can have a sulfur content on a weight basis that is 5000 ppm orless, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm orless, or 10 ppm or less. In another embodiment, the fuel can have asulfur content on a weight basis of 1 to 100 ppm. In one embodiment, thefuel contains 0 ppm to 1000 ppm, or 0 to 500 ppm, or 0 to 100 ppm, or 0to 50 ppm, or 0 to 25 ppm, or 0 to 10 ppm, or 0 to 5 ppm of alkalimetals, alkaline earth metals, transition metals or mixtures thereof. Inanother embodiment, the fuel contains 1 to 10 ppm by weight of alkalimetals, alkaline earth metals, transition metals or mixtures thereof. Itis well known in the art that a fuel containing alkali metals, alkalineearth metals, transition metals or mixtures thereof have a greatertendency to form deposits and therefore foul or plug injectors. The fuelof the invention can be present in a fuel composition in a major amountthat is generally greater than 50 percent by weight, and in otherembodiments is present at greater than 90 percent by weight, greaterthan 95 percent by weight, greater than 99.5 percent by weight, orgreater than 99.8 percent by weight.

Quaternary Ammonium Salt

The composition of the present invention comprises an quaternaryammonium salt which comprises the reaction product of: (a) Mannichreaction product having a tertiary amino group, said Mannich reactionproduct being prepared from the reaction of a hydrocarbyl-substitutedphenol, an aldehyde, and an amine; and (b) a quaternizing agent suitablefor converting the tertiary amino group to a quaternary nitrogen whereinthe quaternizing agent is selected from the group consisting of dialkylsulfates, alkyl halides, hydrocarbyl substituted carbonates; hydrocarbylepoxides in combination with an acid or mixtures thereof.

Examples of quaternary ammonium salt and methods for preparing the sameare described in the following patents, which are hereby incorporated byreference, U.S. Pat. Nos. 4,253,980, 3,778,371, 4,171,959, 4,326,973,4,338,206, and 5,254,138.

Mannich Reaction Product

The Mannich reaction product the present invention has a tertiary aminogroup and is prepared from the reaction product of ahydrocarbyl-substituted phenol, an aldehyde, and an amine.

The hydrocarbyl substituent of the hydrocarbyl-substituted phenol canhave 10 to 400 carbon atoms, in another instance 30 to 180 carbon atoms,and in a further instance 10 or 40 to 110 carbon atoms. This hydrocarbylsubstituent can be derived from an olefin or a polyolefin. Usefulolefins include alpha-olefins, such as 1-decene, which are commerciallyavailable.

The polyolefins which can form the hydrocarbyl substituent can beprepared by polymerizing olefin monomers by well known polymerizationmethods and are also commercially available. The olefin monomers includemonoolefins, including monoolefins having 2 to 10 carbon atoms such asethylene, propylene, 1-butene, isobutylene, and 1-decene. An especiallyuseful monoolefin source is a C₄ refinery stream having a 35 to 75weight percent butene content and a 30 to 60 weight percent isobutenecontent. Useful olefin monomers also include diolefins such as isopreneand 1,3-butadiene. Olefin monomers can also include mixtures of two ormore monoolefins, of two or more diolefins, or of one or moremonoolefins and one or more diolefins. Useful polyolefins includepolyisobutylenes having a number average molecular weight of 400 to3000, in another instance of 400 to 2500, and in a further instance of400 or 500 to 1500. The polyisobutylene can have a vinylidene doublebond content of 5 to 69 percent, in a second instance of 50 to 69percent, and in a third instance of 50 to 95 percent. The polyolefin canbe a homopolymer prepared from a single olefin monomer or a copolymerprepared from a mixture of two or more olefin monomers. Also possible asthe hydrocarbyl substituent source, are mixtures of two or morehomopolymers, two or more copolymers, or one or more homopolymers andone or more copolymers.

The hydrocarbyl-substituted phenol can be prepared by alkylating phenolwith an olefin or polyolefin described above, such as, a polyisobutyleneor polypropylene, using well-known alkylation methods.

The aldehyde used to form the Mannich detergent can have 1 to 10 carbonatoms, and is generally formaldehyde or a reactive equivalent thereofsuch as formalin or paraformaldehyde.

The amine used to form the Mannich detergent can be a monoamine or apolyamine. In either case they will be characterized by the formulaR⁴R⁵NH wherein R⁴ and R⁵ are each independently hydrogen, hydrocarbon,amino-substituted hydrocarbon, hydroxy-substituted hydrocarbon,alkoxy-substituted hydrocarbon, or acylimidoyl groups provided that nomore than one of R⁴ and R⁵ is hydrogen. In all cases, therefore, theywill be characterized by the presence within their structure of at leastone H—N< group. Therefore, they have at least one primary (i.e., H₂N−)or secondary amino (i.e., H—N<) group. Examples of monoamines includeethylamine, dimethylamine, diethylamine, n-butylamine, dibutylamine,allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine,diethanolamine, morpholine, and octadecylamine.

The polyamines from which the detergent is derived include principallyalkylene amines conforming, for the most part, to the formula

wherein t is an integer typically less than 10, A is hydrogen or ahydrocarbyl group typically having up to 30 carbon atoms, and thealkylene group is typically an alkylene group having less than 8 carbonatoms. The alkylene amines include principally, ethylene amines,hexylene amines, heptylene amines, octylene amines, other polymethyleneamines. They are exemplified specifically by: ethylenediamine,diethylenetriamine, triethylene tetramine, propylene diamine,decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamine, trimethylenediamine, pentaethylene hexamine, di(-trimethylene) triamine,aminopropylmorpholine and dimethylaminopropylamine. Higher homologuessuch as are obtained by condensing two or more of the above-illustratedalkylene amines likewise are useful. Tetraethylene pentamine isparticularly useful.

The ethylene amines, also referred to as polyethylene polyamines, areespecially useful. They are described in some detail under the heading“Ethylene Amines” in Encyclopedia of Chemical Technology, Kirk andOthmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950).

In one embodiment, the Mannich detergent can be prepared by reacting ahydrocarbyl-substituted phenol, an aldehyde, and an amine as describedin U.S. Pat. No. 5,697,988. In one embodiment, the Mannich reactionproduct can be prepared from an alkylphenol derived from apolyisobutylene, formaldehyde, and an amine that is a primary monoamine,a secondary monoamine, or an alkylenediamine, in particular,ethylenediamine or dimethylamine.

In another embodiment, the Mannich reaction product of the presentinvention can be prepared by reacting the alkyl-substitutedhydroxyaromatic compound, aldehyde and polyamine by well known methodsincluding the method described in U.S. Pat. No. 5,876,468.

In yet another embodiment, the Mannich reaction product can be preparedby well known methods generally involving reacting the hydrocarbylsubstituted hydroxy aromatic compound, an aldehyde and an amine attemperatures between 50 to 200° C. in the presence of a solvent ordiluent while removing reaction water as described in U.S. Pat. No.5,876,468.

It may be necessary with some of the amines to further react the Mannichreaction product with an epoxide or carbonate or other alkylating agentsto get the tertiary amino group.

Quaternizing Agent

The composition of the present invention contains a quaternizing agentsuitable for converting the tertiary amino group to a quaternarynitrogen wherein the quaternizing agent is selected from the groupconsisting of dialkyl sulfates, alkyl halides, hydrocarbyl substitutedcarbonates; hydrocarbyl epoxides in combination with an acid andmixtures thereof.

In one embodiment, the quaternizing agent can include: halides, such aschloride, iodide or bromide; hydroxides; sulphonates; alkyl sulphates,such as, dimethyl sulfate; sultones; phosphates; C₁₋₁₂ alkylphosphates;di C₁₋₁₂ alkylphosphates; borates; C₁₋₁₂ alkylborates; nitrites;nitrates; carbonates; bicarbonates; alkanoates; O,O-di C₁₋₁₂alkyldithiophosphates; or mixtures thereof.

In one embodiment, the quaternizing agent may be derived from dialkylsulphates such as dimethyl sulfate, N-oxides, sultones such as propaneand butane sultone; alkyl, or arylalkyl halides such as methyl and ethylchloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (oralkyl) substituted carbonates. If the alkyl halide is benzyl chloride,the aromatic ring is optionally further substituted with alkyl oralkenyl groups.

The hydrocarbyl (or alkyl) groups of the hydrocarbyl substitutedcarbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atomsper group. In one embodiment, the hydrocarbyl substituted carbonatescontain two hydrocarbyl groups that may be the same or different.Examples of suitable hydrocarbyl substituted carbonates include dimethylor diethyl carbonate.

In another embodiment, the quaternizing agent can be a hydrocarbylepoxides, as represented by the following formula, in combination withan acid:

wherein R₁, R₂, R₃ and R_(s) can be independently H or a C₁₋₅₀hydrocarbyl group.

Examples of hydrocarbyl epoxides can include: styrene oxide, ethyleneoxide, propylene oxide, butylene oxide, stilbene oxide and C₂₋₅₀epoxide.

Fluidizer

The composition of the present invention can additionally contain afluidizer.

In one embodiment, the fluidizer can be a polyetheramines, which can berepresented by the formula R[OCH₂CH(R¹)]_(n)A, where R is a hydrocarbylgroup, R¹ is selected from the group consisting of hydrogen, hydrocarbylgroups of 1 to 16 carbon atoms, and mixtures thereof, n is a number from2 to about 50, and A is selected from the group consisting of—OCH₂CH₂CH₂NR²R² and —NR³R³, where each R² is independently hydrogen orhydrocarbyl, and each R³ is independently hydrogen, hydrocarbyl or—[R⁴N(R⁵)]_(p)R⁶, where R⁴ is C₂-C₁₀ alkylene, R⁵ and R⁶ areindependently hydrogen or hydrocarbyl, and p is a number from 1-7. Thesepolyetheramines can be prepared by initially condensing an alcohol oralkylphenol with an alkylene oxide, mixture of alkylene oxides or withseveral alkylene oxides in sequential fashion in a 1:2-50 mole ratio ofhydric compound to alkylene oxide to form a polyether intermediate. U.S.Pat. No. 5,094,667 provides reaction conditions for preparing apolyether intermediate, the disclosure of which is incorporated hereinby reference. In one embodiment, the alcohols can be linear or branchedfrom 1 to 30 carbon atoms, in another embodiment 6 to 20 carbon atoms,in yet another embodiment from 10 to 16 carbon atoms. The alkyl group ofthe alkylphenols can be 1 to 30 carbon atoms, in another embodiment 10to 20 carbon atoms. Examples of the alkylene oxides include ethyleneoxide, propylene oxide or butylene oxide. The number of alkylene oxideunits in the polyether intermediate can be 10-35 or 18-27. The polyetherintermediate can be converted to a polyetheramine by amination withammonia, an amine or a polyamine to form a polyetheramine of the typewhere A is —NR³R³. Published Patent Application EP310875 providesreaction conditions for the amination reaction, the disclosure of whichis incorporated herein by reference. Alternately, the polyetherintermediate can also be converted to a polyetheramine of the type whereA is —OCH₂CH₂CH₂NR²R² by reaction with acrylonitrile followed byhydrogenation. U.S. Pat. No. 5,094,667 provides reaction conditions forthe cyanoethylation and subsequent hydrogenation, the disclosure ofwhich is incorporated herein by reference. Polyetheramines where A is—OCH₂CH₂CH₂NH₂ are typically preferred. Commercial examples ofpolyetheramines are the Techron® range from Chevron and the Jeffamine®range from Huntsman.

In another embodiment, the fluidizer can be a polyether, which can berepresented by the formula R⁷O[CH₂CH(R⁸)O]_(q)H, where R⁷ is ahydrocarbyl group, R⁸ is selected from the group consisting of hydrogen,hydrocarbyl groups of 1 to 16 carbon atoms, and mixtures thereof, and qis a number from 2 to about 50. Reaction conditions for preparation aswell as various embodiments of the polyethers are presented above in thepolyetheramine description for the polyether intermediate. A commercialexample of a polyether is the Lyondell ND® series. Other suitablepolyethers are also available from Dow Chemicals, Huntsman, and ICI.

In yet another embodiment, the fluidizer can be a hydrocarbyl-terminatedpoly-(oxyalklene) aminocarbamate as described U.S. Pat. No. 5,503,644.

In yet another embodiment, the fluidizer can be an alkoxylate, whereinthe alkoxylate can comprise: (i) a polyether containing two or moreester terminal groups; (ii) a polyether containing one or more estergroups and one or more terminal ether groups; or (iii) a polyethercontaining one or more ester groups and one or more terminal aminogroups wherein a terminal group is defined as a group located withinfive connecting carbon or oxygen atoms from the end of the polymer.Connecting is defined as the sum of the connecting carbon and oxygenatoms in the polymer or end group.

An alkoxylate can be represented by the formula:

wherein, R¹⁰ is H, TC(O)—, or a C₁₋₃₆ hydrocarbyl group, wherein T is aC₁₋₃₆ fatty acid hydrocarbyl mixture in tallow fatty acid or a fattyacid free of rosin acid; R²⁰ is H, A, WC(O)—, or mixtures thereof,wherein A is selected from the group consisting of —OCH₂CH₂CH₂NR²R² and—NR³R³ where each R² is independently hydrogen or hydrocarbyl, and eachR³ is independently hydrogen, hydrocarbyl or —[R⁴N(R⁵)]_(p)R⁶ where R⁴is C₂-C₁₀ alkylene, R⁵ and R⁶ are independently hydrogen or hydrocarbyl,and p is a number from 1-7, W is a C₁₋₃₆ hydrocarbyl group; R¹ isselected from the group consisting of hydrogen, hydrocarbyl groups of 1to 16 carbon atoms; X is an integer from 1 to 36; Z is an integer 1 to3; Q can be O or N; provided that if Q is N then d can be an integerfrom 0 to 2 and Z is the integer 3-d; if Q is O then d can be an integer0 to 1 and Z is the integer 2-d and if Q is O and R¹ is C₁₋₃₆hydrocarbyl group then R² is WC(O)—.

Examples of the alkoxylate can include: C₁₂₋₁₅ alcohol initiatedpolypropyleneoxide (22-24) ether amine, Bayer ACTACLEAR ND21-A™ (C₁₂-₁₅alcohol initiated polypropyleneoxide (22-24) ether-ol), tall oil fattyacid initiated polypropyleneoxide (22-24) ester-ol, butanol initiatedpolypropyleneoxide (23-25) ether-tallow fatty acid ester, glyceroldioleate initiated polypropyleneoxide (23-25) ether-ol, propylene glycolinitiated polypropyleneoxide (33-34) ether tallow fatty acid ester,tallow fatty acid initiated polypropyleneoxide (22-24) ester-ol andC₁₂-₁₅ alcohol initiated polypropyleneoxide (22-24) ether tallow fattyacid ester.

These alkoxylates can be made from the reaction of a fatty acid such astall oil fatty acids (TOFA), that is, the mixture of fatty acidspredominately oleic and linoleic and contains residual rosin acids ortallow acid that is, the mixture of fatty acids predominately stearic,palmitic and oleic with an alcohol terminated polyether such aspolypropylene glycol in the presence of an acidic catalyst, usuallymethane sulfonic acid. These alkoxylates can also be made from thereaction of glycerol dioleate and propylene oxide in the presence ofcatalyst.

Oil of Lubricating Viscosity

The composition of the present invention can contain an oil oflubricating viscosity. The oil of lubricating viscosity includes naturalor synthetic oils of lubricating viscosity, oil derived fromhydrocracking, hydrogenation, hydrofinishing, unrefined, refined andre-refined oils, or mixtures thereof. In one embodiment, the oil oflubricating viscosity is a carrier fluid for the dispersant and/or otherperformance additives.

Natural oils include animal oils, vegetable oils, mineral oils ormixtures thereof. Synthetic oils include a hydrocarbon oil, asilicon-based oil, a liquid ester of phosphorus-containing acid.Synthetic oils may be produced by Fischer-Tropsch reactions andtypically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.

Oils of lubricating viscosity may also be defined as specified in theAmerican Petroleum Institute (API) Base Oil InterchangeabilityGuidelines. In one embodiment the oil of lubricating viscosity comprisesan API Group I, II, III, IV, V or mixtures thereof, and in anotherembodiment API Group I, II, III or mixtures thereof.

Miscellaneous

The composition optionally comprises one or more additional performanceadditives. The performance additives can include: metal deactivators,detergents, dispersants, viscosity modifiers, friction modifiers,dispersant viscosity modifiers, extreme pressure agents, antiwearagents, antioxidants, corrosion inhibitors, foam inhibitors,demulsifiers, pour point depressants, seal swelling agents, wax controlpolymers, scale inhibitors, gas-hydrate inhibitors, and mixturesthereof.

The total combined amount of the additional performance additivecompounds present on an oil free basis ranges from 0 wt % to 25 wt % or0.01 wt % to 20 wt % of the composition. Although, one or more of theother performance additives may be present, it is common for the otherperformance additives to be present in different amounts relative toeach other.

In one embodiment, the composition can be in a concentrate formingamount. If the present invention may be in the form of a concentrate(which may be combined with additional oil to form, in whole or in part,a finished lubricant and/or liquid fuel), the ratio of the additive ofthe invention and/or other additional performance additives in an oil oflubricating viscosity and/or liquid fuel, to diluent oil is in the rangeof 80:20 to 10:90 by weight.

Antioxidants include molybdenum dithiocarbamates, sulphurised olefins,hindered phenols, diphenylamines; detergents include neutral oroverbased, Newtonian or non-Newtonian, basic salts of alkali, alkalineearth and transition metals with one or more of phenates, sulfurizedphenates, sulfonates, carboxylic acids, phosphorus acids, mono- and/ordi-thiophosphoric acids, saligenins, an alkylsalicylates, salixarates.

Dispersants include N-substituted long chain alkenyl succinimide as wellas posted treated version thereof, post-treated dispersants includethose by reaction with urea, thiourea, dimercaptothiadiazoles, carbondisulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substitutedsuccinic anhydrides, nitriles, epoxides, boron compounds, and phosphoruscompounds.

Antiwear agents include: metal thiophosphates, especially zincdialkyldithiophosphates; phosphoric acid esters or salt thereof;phosphites; and phosphorus-containing carboxylic esters, ethers, andamides.

Anti-scuffing agents include: organic sulfides and polysulfides, suchas, benzyldisulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide,di-tertiary butyl polysulfide, di-tert-butylsulfide, sulfurizedDiels-Alder adducts or alkyl sulfenyl N′N-dialkyl dithiocarbamates.

Extreme Pressure (EP) agents include: chlorinated wax; organic sulfidesand polysulfides, such as, benzyldisulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid,sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, andsulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons; andmetal thiocarbamates, such as, zinc dioctyldithiocarbamate.

Friction modifiers include: fatty amines; esters, such as, boratedglycerol esters; partial esters of glycerol, such as, glycerolmonooleate; fatty phosphites; fatty acid amides; fatty epoxides; boratedfatty epoxides; alkoxylated fatty amines; borated alkoxylated fattyamines; metal salts of fatty acids; fatty imidazolines; condensationproducts of carboxylic acids and polyalkylene-polyamines; and aminesalts of alkylphosphoric acids.

Viscosity modifiers include: hydrogenated copolymers ofstyrene-butadiene, ethylene-propylene polymers, polyisobutenes,hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers,polymethacrylate acid esters, polyacrylate acid esters, polyalkylstyrenes, alkenyl aryl conjugated diene copolymers, polyolefins,polyalkylmethacrylates and esters of maleic anhydride-styrenecopolymers.

Dispersant viscosity modifiers (often referred to as DVM) include:functionalized polyolefins, for example, ethylene-propylene copolymersthat have been functionalized with the reaction product of maleicanhydride and an amine; a polymethacrylate functionalized with an amine;and styrene-maleic anhydride copolymers reacted with an amine.

Corrosion inhibitors include: octylamine octanoate; condensationproducts of dodecenyl succinic acid or anhydride and a fatty acid, suchas, oleic acid with a polyamine.

Metal deactivators include: derivatives of dimercaptothiodiazole,1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or2-alkyldithiobenzothiazoles.

Foam inhibitors include copolymers of ethyl acrylate and2-ethylhexylacrylate and optionally vinyl acetate.

Demulsifiers include polyethylene glycols, polyethylene oxides,polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pourpoint depressants including esters of maleic anhydride-styrene,polymethacrylates, polyacrylates or polyacrylamides.

Seal swell agents include Exxon Necton-37™ (FN 1380) and Exxon MineralSeal Oil.

INDUSTRIAL APPLICATION

In one embodiment, the present invention is useful as a liquid fuel foran internal combustion engine. The internal combustion engine includesspark ignition and compression ignition engines; 2-stroke or 4-strokecycles; liquid fuel supplied via direct injection, indirect injection,port injection and carburetor; common rail and unit injector systems;light (e.g. passenger car) and heavy duty (e.g. commercial truck)engines; and engines fuelled with hydrocarbon and non-hydrocarbon fuelsand mixtures thereof. The engines may be part of integrated emissionssystems incorporating such elements as; EGR systems; aftertreatmentincluding three-way catalyst, oxidation catalyst, NOx absorbers andcatalysts, catalyzed and non-catalyzed particulate traps optionallyemploying fuel-borne catalyst; variable valve timing; and injectiontiming and rate shaping.

In another embodiment, the present invention is useful in coatings,inks, millbases, plastics and paints, especially high solids paints;inks, especially offset, gravure and screen inks, radiation curableinks; non-aqueous ceramic processes, especially tape-coating,doctor-blade, extrusion and injection moulding type processes;composites, cosmetics, adhesives and plastics materials. Additionally,the composition of the present invention is an effective dispersant foruniformly distributing a particulate solid in an organic medium.Examples of suitable particulate solids are pigments for solvent inks;pigments, extenders and fillers for paints and plastics materials;disperse dyes; optical brightening agents and textile auxiliaries forsolvent dyebaths, inks and other solvent application systems; solids foroil-based and inverse-emulsion drilling muds; dirt and solid particlesin dry cleaning fluids; particulate ceramic materials; magneticmaterials and magnetic recording media; fibres such as glass, steel,carbon and boron for composite materials; and biocides, agrochemicalsand pharmaceuticals which are applied as dispersions in organic media.

In one embodiment, the invention provides a composition comprising (i) aparticulate solid; (ii) an organic medium; and (iii) a quaternaryammonium salt which comprises the reaction product of:

a. Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

In one embodiment, the organic medium is an organic liquid or a plasticsmaterial.

In one embodiment, the composition as claimed in claim 1 wherein theorganic liquid comprises at least 0.1% by weight of a polar organicliquid based on the total organic liquid.

In one embodiment, the particulate solid is a pigment.

In one embodiment, the invention provides a paint or ink compositioncomprising a particulate solid, an organic liquid, a binder and aquaternary ammonium salt which comprises the reaction product of:

a. Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The binder is a polymeric material capable of binding the composition onvolatilisation of the organic liquid. Binders are polymeric materialsincluding natural and synthetic materials. In one embodiment, bindersinclude poly(meth)acrylates, polystyrenics, polyesters, polyurethanes,alkyds, polysaccharides such as cellulose, and natural proteins such ascasein. In one embodiment, the binder can be present in the compositionat more than 100% based on the amount of particulate solid, more than200%, more than 300% or more than 400%.

In one embodiment, the invention provides a mill-base comprising aparticulate solid, an organic liquid and a quaternary ammonium saltwhich comprises the reaction product of:

a. Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

In one embodiment, the solid is an organic pigment from any of therecognised classes of pigments described, for example, in the ThirdEdition of the Colour Index (1971) and subsequent revisions of, andsupplements thereto, under the chapter headed “Pigments”. Examples oforganic pigments are those from the azo, disazo, condensed azo,thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone,isodibenzanthrone, triphendioxazine, quinacridone and phthalocyanineseries, especially copper phthalocyanine and its nuclear halogenatedderivatives, and also lakes of acid, basic and mordant dyes. Carbonblack, although strictly inorganic, behaves more like an organic pigmentin its dispersing properties. In one embodiment, the organic pigmentsare phthalocyanines, especially copper phthalocyanines, monoazos,disazos, indanthrones, anthranthrones, quinacridones and carbon blacks.

Inorganic solids include: extenders and fillers, such as, talc, kaolin,silica, barytes and chalk; particulate ceramic materials, such as,alumina, silica, zirconia, titania, silicon nitride, boron nitride,silicon carbide, boron carbide, mixed silicon-aluminium nitrides andmetal titanates; particulate magnetic materials, such as, the magneticoxides of transition metals, especially iron and chromium, e.g.gamma-Fe₂O₃, Fe₃O₄, cobalt-doped iron oxides, calcium oxide, ferrites,especially barium ferrites; and metal particles, especially metalliciron, nickel, cobalt, copper and alloys thereof.

In one embodiment, the organic medium, which can be present with thecomposition of the reaction product of the invention and particulatesolid, is a plastics material. In another embodiment the organic mediumcan be an organic liquid. The organic liquid may be a non-polar or apolar organic liquid. In one embodiment, non-polar organic liquids arecompounds containing aliphatic groups, aromatic groups or mixturesthereof. The non-polar organic liquids include non-halogenated aromatichydrocarbons (e.g. toluene and xylene), halogenated aromatichydrocarbons (e.g. chlorobenzene, dichlorobenzene, chlorotoluene),non-halogenated aliphatic hydrocarbons (e.g. linear and branchedaliphatic hydrocarbons containing six or more carbon atoms both fullyand partially saturated), halogenated aliphatic hydrocarbons (e.g.dichloromethane, carbon tetrachloride, chloroform, trichloroethane) andnatural non-polar organics (e.g. vegetable oil, sunflower oil, linseedoil, terpenes and glycerides). In one embodiment, thermoplastic resinsinclude: polyolefins, polyesters, polyamides, polycarbonates,polyurethanes, polystyrenics, poly(meth)acrylates, celluloses andcellulose derivatives. The compositions may be prepared in a number ofways but melt mixing and dry solid blending are typical methods. Ifdesired, the compositions may contain other ingredients, for example,resins (where these do not already constitute the organic medium),binders, fluidizing agents anti-sedimentation agents, plasticisers,surfactants, anti-foamers, rheology modifiers, leveling agents, glossmodifiers and preservatives.

A dispersion may be prepared by any of the conventional methods knownfor preparing dispersions. Thus, the particulate solid, the organicmedium, and the dispersant may be mixed in any order, the mixture thenbeing subjected to a mechanical treatment to reduce the particles of thesolid to an appropriate size, for example, by ball milling, beadmilling, gravel milling or plastic milling until the dispersion isformed. Alternatively, the solid may be treated to reduce its particlesize independently or in admixture with either the organic medium or thedispersant, the other ingredient or ingredients then being added and themixture being agitated to provide the composition.

The composition of the present invention is particularly suited toliquid dispersions. In one embodiment, such dispersion compositionscomprise:

-   -   (a) from 0.5 to 70 parts of a particulate solid;    -   (b) from 0.5 to 30 parts of a compound of the quaternary        ammonium salt described above; and    -   (c) from 20 to 99 parts of an organic liquid; wherein all parts        are by weight and the amounts (a)+(b)+(c)=100.        and such dispersions are useful as (liquid) inks, paints, and        mill-bases.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form aring); substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

EXAMPLES

The invention will be further illustrated by the following examples,which sets forth particularly advantageous embodiments. While theexamples are provided to illustrate the present invention, they are notintended to limit it.

The detergents of the present invention are evaluated in the modifiedASTM D5500 Driving Cycle Test. The vehicles used in this test are BMW™318i automobiles with 1.8 L 4 cycle engines. The fuel is a regularunleaded subgrade 85 octane blended with 10% ethanol. A polyether basedfluidizer is included in the compositions. The intake valves are BMW™intake valve model number 11-34-1-254-625.

The detergents that are used in this test include: a commercialavailable mannich reaction product of a 1000 Mn polyisobutylene phenol,formaldehyde and, dimethylamine (Comparative Example 1), and theexperimental detergent of the present invention (Example 1) as describedbelow.

Preparatory Example A:

Preparatory Example A is prepared from a mixture of alkylated phenolprepared from 1000 Mn polyisobutylene (800 grams) and diluent oil—SO-44(240 grams) nitrogen is applied and the mixture is stirred at 100 rpm.To this mixture, Formalin (55.9 grams) is added (dropwise) over 50minutes. After which, dimethylamine (73.3 grams) is added (dropwise)over the next 50 minutes. The entire mixture is heated to 68° C. andheld at 68° C. for one hour. After one hour, the mixture is heated to106° C. and held for a further 2 hours. The temperature of the mixtureis increased to 130° C. and held for 30 minutes before coolingovernight. The mixture is purified by vacuum distillation (130° C., −0.9bar) to remove any remaining water. The resulting compound is a DMAMannich.

Example 1

Reaction product of Preparatory Example A (1700 grams), styrene oxide(263 grams), acetic acid (66 grams) and methanol (4564 grams) are heatedwith stirring to reflux (˜75° C.) for 6.5 hours under a nitrogenatmosphere. The reaction is purified by distillation (30° C., −0.8 bar).The resulting compound is a styrene oxide quaternary ammonium salt.

Note: For Comparative Example 1 the active chemical is accompanied byinert diluent oil in a ratio of active chemical to diluent oil of about75:25 by weight.

Note: For Examples 1 the active chemical is accompanied by inert diluentoil in a ratio of active chemical to diluent oil of about 75:25 byweight.

TABLE 1 Results in the ASTM D5500 Driving Cycle Test Detergent Dose RateActive (PTB) mg/valve Comparative Example 1 12.5 55.0 ComparativeExample 1 12.5 84.0 Comparative Example 1 25.0 18.7 Example 1 12.5  5.0Example 1 12.5 48.0 Example 1  8.4 64.0

The results of the test show that formulations using quaternary ammoniumsalt detergents of the present invention (Example 1) show equivalent orsuperior reduction in deposit formation of an intake valve injectorcompared to a commercially available detergent (Comparative Examples 1).

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of” permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

1. A method of fueling an internal combustion engine comprising: A.supplying to said engine a fuel composition comprising: i. a fuel whichis liquid at room temperature; and ii. quaternary ammonium saltcomprising the reaction product of: a. Mannich reaction product having atertiary amino group, said Mannich reaction product being prepared fromthe reaction of a hydrocarbyl-substituted phenol, an aldehyde, andamine; and b. a quaternizing agent suitable for converting the tertiaryamino group to a quaternary nitrogen wherein the quaternizing agentcomprises hydrocarbyl substituted carbonates, hydrocarbyl epoxides incombination with an acid, and mixtures thereof.
 2. A method oflubricating an internal combustion engine comprising: A. supplying tothe crankcase of said engine a lubricating composition comprising: i. anoil of lubricating viscosity; and ii. quaternary ammonium saltcomprising the reaction product of: a. Mannich reaction product having atertiary amino group, said Mannich reaction product being prepared fromthe reaction of a hydrocarbyl-substituted phenol, an aldehyde, andamine; and b. a quaternizing agent suitable for converting the tertiaryamino group to a quaternary nitrogen wherein the quaternizing agentcomprises hydrocarbyl substituted carbonates, hydrocarbyl epoxides incombination with an acid, and mixtures thereof.
 3. A compositioncomprising: (i) a particulate solid; (ii) an organic medium; and (iii) aquaternary ammonium salt which comprises the reaction product of: a.Mannich reaction product having a tertiary amino group, said Mannichreaction product being prepared from the reaction of ahydrocarbyl-substituted phenol, an aldehyde, and an amine; and b.quaternizing agent suitable for converting the tertiary amino group to aquaternary nitrogen wherein the quaternizing agent comprises hydrocarbylsubstituted carbonates, hydrocarbyl epoxides in combination with anacid, and mixtures thereof.
 4. The composition of claim 3, wherein theorganic medium is an organic liquid or a plastics material.
 5. Thecomposition of claim 3, wherein the organic liquid comprises at least0.1% by weight of a polar organic liquid based on the total organicliquid.
 6. The composition of claim 3, wherein the particulate solid isa pigment.
 7. A paint or ink composition comprising a particulate solid,an organic liquid, a binder and a quaternary ammonium salt whichcomprises the reaction product of: a. Mannich reaction product having atertiary amino group, said Mannich reaction product being prepared fromthe reaction of a hydrocarbyl-substituted phenol, an aldehyde, and anamine; and b. quaternizing agent suitable for converting the tertiaryamino group to a quaternary nitrogen wherein the quaternizing agentcomprises hydrocarbyl substituted carbonates, hydrocarbyl epoxides incombination with an acid, and mixtures thereof.
 8. A mill-basecomprising a particulate solid, an organic liquid and a quaternaryammonium salt which comprises the reaction product of: a. Mannichreaction product having a tertiary amino group, said Mannich reactionproduct being prepared from the reaction of a hydrocarbyl-substitutedphenol, an aldehyde, and an amine; and b. quaternizing agent suitablefor converting the tertiary amino group to a quaternary nitrogen whereinthe quaternizing agent comprises hydrocarbyl substituted carbonates,hydrocarbyl epoxides in combination with an acid, and mixtures thereof.9. The method of claim 1, wherein the hydrocarbyl substituent of thehydrocarbyl-subsituted phenol of component (a) is a polyolefin having anumber average molecular weight of 400 to 3,000; wherein the aldehyde ofcomponent (a) is a formaldehyde or a reactive equivalent thereof; andwherein the amine of component (a) is selected from the group consistingof di-methylamine, ethylenediamine, dimethylaminopropylamine,diethylenetriamine, dibutylamine, and mixtures thereof.
 10. The methodof claim 1, wherein said fuel composition further comprises a fluidizer.11. The method of claim 2, wherein the hydrocarbyl substituent of thehydrocarbyl-subsituted phenol of component (a) is a polyolefin having anumber average molecular weight of 400 to 3,000; wherein the aldehyde ofcomponent (a) is a formaldehyde or a reactive equivalent thereof; andwherein the amine of component (a) is selected from the group consistingof di-methylamine, ethylenediamine, dimethylaminopropylamine,diethylenetriamine, dibutylamine, and mixtures thereof.
 12. The methodof claim 2, wherein said lubricating composition further comprises oneor more metal deactivators, detergents other than those of claim 14,dispersants, viscosity modifiers, friction modifiers, dispersantviscosity modifiers, extreme pressure agents, antiwear agents,antioxidants, corrosion inhibitors, foam inhibitors, demulsifiers, pourpoint depressants, seal swelling agents, wax control polymers, scaleinhibitors, gas-hydrate inhibitors and mixtures thereof.
 13. Thecomposition of claim 3, wherein the hydrocarbyl substituent of thehydrocarbyl-subsituted phenol of component (a) is a polyolefin having anumber average molecular weight of 400 to 3,000; wherein the aldehyde ofcomponent (a) is a formaldehyde or a reactive equivalent thereof; andwherein the amine of component (a) is selected from the group consistingof di-methylamine, ethylenediamine, dimethylaminopropylamine,diethylenetriamine, dibutylamine, and mixtures thereof.
 14. The paint orink composition of claim 7, wherein the hydrocarbyl substituent of thehydrocarbyl-subsituted phenol of component (a) is a polyolefin having anumber average molecular weight of 400 to 3,000; wherein the aldehyde ofcomponent (a) is a formaldehyde or a reactive equivalent thereof; andwherein the amine of component (a) is selected from the group consistingof di-methylamine, ethylenediamine, dimethylaminopropylamine,diethylenetriamine, dibutylamine, and mixtures thereof.
 15. Themill-base of claim 8, wherein the hydrocarbyl substituent of thehydrocarbyl-subsituted phenol of component (a) is a polyolefin having anumber average molecular weight of 400 to 3,000; wherein the aldehyde ofcomponent (a) is a formaldehyde or a reactive equivalent thereof; andwherein the amine of component (a) is selected from the group consistingof di-methylamine, ethylenediamine, dimethylaminopropylamine,diethylenetriamine, dibutylamine, and mixtures thereof.